DE3426792A1 - METHOD FOR PRODUCING MONOPEROXYDICARBONIC ACIDS AND THE SALTS THEREOF - Google Patents

Description

Degussa Aktiengesellschaft Weissfrauenstrasse 9, 6000 Frankfurt am Main

Process for the preparation of monoperoxydicarboxylic acids and their salts

The invention relates to the production of monoperoxydicarboxylic acids and their salts. The use of these compounds as bleaching agents in laundry detergents has long been used known.

In the AU-PS 417 480 the improved bleaching effect of monoperoxyphthalic acid in the presence

2+
of Mg ions in the bleaching liquor.

FR-PS 2 129 034 relates to the production of stable monoperoxyphthalic acid from phthalic anhydride and hydrogen peroxide, in the presence of from 0/01 to 1 mole of magnesium oxide, per mole of anhydride.

The peracid is precipitated from the at least partially formed Mg salt of the peracid by adding a strong mineral acid. According to EP-B1-0 027 69 3, an alkaline magnesium compound is also required in order to carry out the oxidation of phthalic anhydride with hydrogen peroxide and at the same time to obtain the magnesium salt of monoperoxyphthalic acid.
The production of monoperoxyphthalic acid is carried out in Acta chem.Scand. J_2 (1958) 6, 1331. In order to achieve a sufficient yield, it is necessary to react the phthalic anhydride with the alkaline oxidation solution at a temperature below -5 ° C. After adding sulfuric acid and water to the solution, the peracid is separated off by extraction with ether.

3426732

The object of the invention is a method to easily Ways to obtain monoperoxydicarboxylic acids and their salts.

The invention relates to a process for the preparation of monoperoxydicarboxylic acids (hereinafter referred to as Peracids) and their salts by oxidation of the corresponding anhydrides with hydrogen peroxide in an organic solvent which dissolves the resulting peracids, characterized in that the Oxidation in the presence of an anion exchanger takes place, after the reaction the anion exchanger separated and the monoperoxydicarboxylic acid isolated from the solution or the corresponding salt

¹ ^ precipitates due to the addition of an alkaline alkali or alkaline earth compound.

As anhydrides, there are compounds of the following

Formulas used:
20th

a) Formula (I):
¹⁰ ^

in which mean the same or different

1 2
R, R; Hydrogen,

C - C ₁₀ alkyl, linear or branched, η: o; 1 to 10, in particular 0 to 2, the anhydrides of glutaric acid, succinic acid and their monoalkylated derivatives are preferred,

the alkyl group of which has 1 to 18 carbon atoms. b) Formula (II)

.2 /

C ti 0

1 in which R and R have the same meaning as above, preferred are the anhydrides of maleic acid, Citraconic acid

c) Formula III

in the mean 6

R ³ ,

R ⁵ ,

R ", identical or different,

. _n alkyl, linear or branched,

Hydrogen, C ₁ - C the sulfonate or nitro group, chlorine or bromine,

3 4 4 5 5 or R and R, or R and R or R and R are omitted, and between the respective ring carbon atoms there is a double bond.

The anhydrides of cyclohexane are preferred dicarboxylic acid (1.2.), 4Methylcyclohexan-1.2-dicarboxylic acid 4-cyclohexane-1,2-dicarboxylic acid _t

or

d) Formula IV

in the mean

7 8 9 10
R, R, R and R, identical or different, hydrogen, C. -

₀ alkyl, linear or branched, the sulfonate or nitro group and chlorine or bromine.

The anhydride of o-phthalic acid is preferably used,

Hydrogen peroxide is used in the form of aqueous solutions, their peroxide concentration from 20 to 99%, preferably from 40 to 60% by weight.

The embodiment in which the water content of the oxidation mixture is not yet particularly suitable is particularly suitable leads to emulsification with the solvent.

Hydrogen peroxide is used in a stoichiometric ratio of 1: 1 to the anhydride. An easy one

Excess of up to 0.2 mol, preferably 0.1 mol
However, hydrogen peroxide is beneficial.

The range for the quantity ratio more basic
Ion exchanger to anhydride ranges from 0.1g to
50 g, preferably 10 g to 20 g, ion exchanger
per mole of anhydride.

Basic ion exchangers can be used, preferably weakly basic ones, provided that
that they are stable to oxidation.

This information can be used without difficulty
Take the data sheets of the commercially available ion exchangers.

In contrast to processes according to the prior art, the use of the ion exchanger makes it possible the continuous production of the peracids according to the invention by, for example, the reaction mixture brought into contact with the ion exchanger on a distance sufficient for the conversion.

In the process according to the invention, there is no prior art presence
common basic salts such as alkali or
Alkaline earth hydroxides or basic carbonates

and the monoperoxycarboxylic acid directly without the addition of mineral acid.

The preparation of these acids has hitherto been made difficult by the fact that the most suitable time of the Could not accurately predict acidification of the reaction mixture.

If a salt of the peracid is desired, the remaining salt is added after the ion exchanger has been separated off

Reaction solution an alkali or alkaline earth oxide, hydroxide or carbonate, preferably magnesium compound, in an amount that is theoretically sufficient to neutralize the remaining carboxy group, preferably in an excess of 1%. The particularly suitable magnesium hydroxide is in a molar ratio of at least 1: 2, based on the peracid, is used. Particularly suitable magnesium hydroxide / peracid ratios are from 1: 2 to 1.1:

In the case of monoperoxyphthalic acid, this occurs hydrated salt

0 C-OH

C-O *

Mg '

The order of addition of anhydride and anion exchanger to the organic solvent is not decisive.

However, it is important that the temperature be controlled when the anhydride and hydrogen peroxide are reacted. The reaction temperature is in the range from -10 ⁰ C to 50 C, preferably 0 C

to 20 ⁰ C, in particular 10 ° C to 20 ° C.

The reaction time should be 5 minutes to 5 hours, preferably 10 minutes to 1 hour.

The reaction between the alkaline or alkaline earth metal compound and the alkali Monoperoxydicarbonsäure formed is preferably carried out between 15 min and 20 ° C ⁰ C with a reaction time 2 to 20

The resulting salt of the peracid is then separated according to the rules of technology e.g. via filters or centrifuges. Subsequently, it is preferred with non-aqueous solvents washed to dissolve any remaining anhydride.

Aliphatic esters with a low molecular weight are preferably used as the organic solvent Acetates and especially ethyl acetate. Good solvency is important for the selection the solvent for the resulting peracid. 20th

The anhydride used must at least be partially dissolved, the alkali or alkaline earth salts of the Peracids do not dissolve in the solvent used 25

example 1

25 g of phthalic anhydride are added to 150 ml of ethyl acetate loosened and cooled to 10 C. Then 3 g of Lewatit MP 62 are added. Subsequently, within 15 min 11.5 g of 50% by weight hydrogen peroxide were added dropwise at the same temperature and with stirring. so the mixture is subsequently stirred for 1 h, the temperature of the batch rising to approx. Then you separate the ion exchanger and wins from the solution 25.4 g of monoperoxyphthalic acid with an AO content of 7.0%.

Example 2

25 g of phthalic anhydride are dissolved in 150 ml of ethyl acetate and cooled ^{to 10 ° C.} Then 3 g of Lewatit MP 62 are added. 11.5 g of 50% by weight hydrogen peroxide are then added dropwise over the course of 15 minutes at the same temperature and with stirring. The mixture is then stirred for a further 1 hour, the temperature of the batch rising to approx. The ion exchanger is then separated off and, after neutralization with 5 g of magnesium hydroxide at 20 ° C. in 15 minutes and drying, 31 g of hydrated monoperoxyphthalic acid mono-Mg salt with an AO content of 5.1%.

Example 3

25 g of phthalic anhydride are dissolved in 150 ml of ethyl acetate and cooled ^{to 10 ° C.} Then 3 g of Lewatit MP 62 are added. 11.5 g of 50% by weight hydrogen peroxide are then added over the course of 15 minutes

the same temperature and added dropwise with stirring. The mixture is then stirred for 3 h, the temperature of the batch rises to approx. 20 C. The ion exchanger is then separated off and recovered after neutralization with 5 g Magnesium hydroxide at 20 ° C. in 15 min and drying 27 g of hydrated monoperoxyphthalic acid mono-Mg salt with an AO content of 5.4%.

Example 4

25 g of phthalic anhydride are dissolved in 150 ml of ethyl acetate and heated to 20 ° C. Then add 3 g Lewatit MP 62 added. Subsequently, within

15 min 11.5 g of 50% by weight hydrogen peroxide were added dropwise at the same temperature and with stirring. The mixture is then stirred at this temperature for 1 h. Thereafter, the ion exchanger is separated off and gains after neutralization with 5 g of magnesium hydroxide at 20 ⁰ C in 15 minutes and drying 23 g of hydrated monoperoxyphthalic acid-mono-Mg salt with an AO content of 5.2%.

Example 5

25 g of phthalic anhydride are dissolved in 100 ml of ethyl acetate and heated to 20 ° C. Then add 3 g Lewatit MP 62 added. 11.5 g of 50% by weight hydrogen peroxide are then added over the course of 15 minutes added dropwise at the same temperature and with stirring. The mixture is then stirred at 30 ° C. for 1 h. The ion exchanger is then separated off and recovered after neutralization with 5 g of magnesium hydroxide at 20 ° C. in 15 min and drying 25 g of hydrated monoperoxyphthalic acid mono-Mg salt with an AO content of 5.2%.

Example 6

25 g of phthalic anhydride are dissolved in 150 ml of ethyl acetate loosened and cooled to 10 C. Then 1 g of Lewatit MP 62 is added. Then within 11.5 g of 50% by weight hydrogen peroxide were added dropwise over a period of 15 minutes at the same temperature and with stirring.

The mixture is then stirred for 1 h, the temperature

ο
of the approach rises to approx. Thereafter, the ion exchanger is separated off and gains after neutralization with 5 g of magnesium hydroxide at 20 ⁰ C in 15 minutes and drying 25 g of hydrated monoperoxyphthalic acid-mono-Mg salt with an AO content of 5.4%.

Example 7

25 g of phthalic anhydride are dissolved in 150 ml of ethyl-20

acetate dissolved and cooled to 10 ° C. Then 3 g of Lewatit MP 62 are added. 11.5 g of 50% by weight hydrogen peroxide are then added dropwise over the course of 15 minutes at the same temperature and with stirring. Well 1 h, stirring is continued, keeping the temperature of the mixture to ca "rises 20 ⁰ C.

Thereafter, the ion exchanger is separated off and gains to neutralization with 3.4 g of magnesium oxide at 20 ⁰ C in 15 minutes and drying 23 g of hydrated monoperoxyphthalic acid-mono-salt with a Mg-

g ₀ AO content of 5.2%.

Example 8

25 g of phthalic anhydride are dissolved in 150 ml of ethyl acetate loosened and cooled to 10 ° C. Then 3 g of Lewatit MP 62 are added. Then within 11.5 g of 50% by weight hydrogen peroxide were added dropwise over a period of 15 minutes at the same temperature and with stirring. The mixture is then stirred for a further 1 hour, the temperature of the batch rising to approx. 20 ° C. Then separate the ion exchanger is removed and, after neutralization with 9.8 g of basic magnesium carbonate, is obtained 20 C in 15 min and drying 12 g of hydrated monoperoxyphthalic acid mono-Mg salt with a AO content of 2.3%.

Example 9

25 g of phthalic anhydride are dissolved in 150 ml of ethyl acetate and cooled to 10 ° C. Then 3 g of Lewatit MP 62 are added. Then, over the course of 15 minutes, 20 g of 30% by weight hydrogen peroxide are added dropwise at the same temperature and with stirring. The mixture is then stirred for a further 1 hour, the temperature of the batch rising to approx. Thereafter, the ion exchanger is separated off and gains after neutralization with 5 g of magnesium hydroxide at 20 ° C in 15 minutes and drying 18 g hydrated monoperoxyphthalic acid-mono-Mg-salt having a content of ^AO-4 '· ^9%

-ie- 3 A? β 7 O

Example 10

25 g of phthalic anhydride are dissolved in 100 ml of ethyl acetate and cooled to 1O ⁰ C. Then 3 g c Lewatit MP 62 are added. Then 15 g of 40% by weight hydrogen peroxide are added dropwise at the same temperature and with stirring over the course of 15 minutes. Well 1 is stirred h, wherein the temperature of the mixture rises to about 20 ⁰ C. Thereafter, the ion exchanger is separated off and gains after neutralization with 5 g of magnesium hydroxide at 20 ⁰ C in 15 minutes and drying 25 g of hydrated Monoperoxyphthaisäuremono-Mg-salt with an AO content of 5.3%.

Example 11

16/7 g of maleic anhydride are dissolved in 150 ml of ethyl acetate loosened and cooled to 0 ° C. Then 3 g of Lewatit MP 62 are added. Then within

from 10 min 11.5 g of 50% by weight hydrogen peroxide the same temperature and added dropwise with stirring. The mixture is then stirred for 1 h, the temperature is kept between 0 and 5 ° C. The ion exchanger is then separated off and obtained from the Solution 16 g of monoperoxymaleic acid with an AO content of 10.8%.

Example 12

19.4 g of glutaric anhydride are dissolved in 150 ml of ethyl acetate and cooled ^{to 10 ° C.} Then 3 g of Lewatit MP 62 are added. 11.5 g of 50% by weight hydrogen peroxide are then added dropwise at the same temperature and with stirring over the course of 5 minutes.

The mixture is then stirred for a further 1 hour, the temperature of the batch rising to approx. Then you separate the ion exchanger and wins from the solution 21 g Monoperoxyglutaric acid with an AO content of 6.7%.

Example 13

26.2 g of cyclohexane-1,2-dicarboxylic anhydride ΙΟ are dissolved in 150 ml of ethyl acetate and cooled to 10 ⁰ C. Then 3 g of Lewatit MP 62 are added. 11.5 g of 50% by weight hydrogen peroxide are then added dropwise over the course of 5 minutes at the same temperature and with stirring. The mixture is then stirred for a further 1 hour, the temperature rising to approx. The ion exchanger is then separated off and 25 g of monoperoxycyclohexane-1,2-dicarboxylic acid with an AO content of 4.0% are obtained from the solution.

Example 14

28.6 g of 4-methylcyclohexane-1,2-dicarboxylic anhydride are dissolved in 150 ml of ethyl acetate and cooled to 10 ⁰ C. Then 3 g of Lewatit MP 62 are added. 11.5 g of 50% by weight hydrogen peroxide are then added dropwise over the course of 5 minutes at the same temperature and with stirring. Well 1 h, stirring is continued while the temperature rises to about 20 ⁰ C. The ion exchanger is then separated off and 28 g of monoperoxy-4-methylcyclohexane-1,2-dicarboxylic acid with an AO content of 4.0% are obtained from the solution.

- ie - 3428792

Example 15

36.1 g of octylsuccinic anhydride are dissolved in 150 ml of ethyl acetate and cooled to 10.degree. Then 3 g of Lewatit MP 62 are added. 11.5 g of 50% by weight hydrogen peroxide are then added dropwise at the same temperature and with stirring over the course of 5 minutes. The mixture is then subsequently stirred for 1 h, the temperature rising ^{to approx. 20 ° C.} The ion exchanger is then separated off and 37 g of monoperoxy-2-octy / succinic acid with an AO content of 3.5% are obtained from the solution.

Example 16

14.8 g tetradecylsuccinic anhydride are dissolved in 100 ml of ethyl acetate and cooled to 10 ⁰ C. Then 1 g of Lewatit MP 62 is added. 3.4 g of 50% by weight hydrogen peroxide are then added dropwise over the course of 10 minutes at the same temperature and with stirring. The mixture is then subsequently stirred for 3 hours, the temperature rising to approx. The ion exchanger is then separated off and 9 g of mono-

2π peroxy-2-tetradecylsuccinic acid with a AO content of 2.7%.

Claims (6)

07/19/1984 84 164 PV Degussa Aktiengesellschaft Weissfrauenstrasse 9, 6000 Frankfurt am Main Process for the preparation of monoperoxydicarboxylic acids and their salts Patent claims: 1J Process for the preparation of monoperoxydicarboxylic acids and their alkali or alkaline earth salts by oxidation of the corresponding anhydrides with Hydrogen peroxide in an organic solvent which dissolves the resulting peracids, characterized in that the oxidation is carried out in the presence of an anion exchanger, after the reaction has taken place, the anion exchanger is separated off and the monoperoxydicarboxylic acid is removed from the Solution isolated or the corresponding monosalt by adding an amount of an alkaline Alkali or alkaline earth compound precipitates, which is sufficient, the resulting non-peroxidized Neutralize carboxyl group. 2. The method according to claim 1, characterized in that anhydrides of the formulas are oxidized: Formula (I) R ¹ i I * η / (CH-) Ό
| 2 η _ 2 - in which mean the same or different 1 2 R ζ R: hydrogen, C ₁ -C ₁₀ alkyl, linear or I Ί ο branched, η: ο to Π ι, ο ς 7 Ö <4 Λ -J ι or
Formula (II) R ^{2 /} 'C- 1 2 R, R: hydrogen; C _{1 -C 1g} alkyl, linear or branched or (III) R ⁴ R ³
φ - \
O 20th formula R ⁶ 25th in which are R, R, R, R, identical or different, Hydrogen, C _{1 -C 10} alkyl, linear or branched, the sulfonate or nitro group and chlorine or Bromine, 3 4 4 5 5 Or R and R, or R and R or R and R omitted, and between the respective ring carbon atoms there is a double bond, or R ⁸ - R ⁷
ι 3 - Formula IV R ⁹ / ΓςΧ 0
Il k ¹⁰ ■ ^c \
0 Ve »
II 0 3425732 in the mean 7 8 Q 1Π R / R / R and R, identical or different, hydrogen, C. - C ₁₀ alkyl, linear or branched, the sulfonate or nitro group, chlorine or bromine. 3. The method according to claim 2, characterized in that phthalic anhydride is used. 4. The method according to claims 1 to 3, characterized characterized in that the peracid formation at a temperature of -10 C to 50 C, is preferred from 0 C to 20 C, a reaction time from 5 min to 5 h, preferably 10 min to 1 h, a hydrogen peroxide / anhydride ratio from 1: 1 to 1.2: 1, preferably 1.1: 1, in ethyl acetate. 5. The method according to claims 1 to 4, characterized characterized in that one has an alkaline effect to form a salt of the monoperoxycarboxylic acid inorganic magnesium compound is used. 6. The method according to claim 5, characterized in that there is a magnesium hydroxide / peracid molar ratio selects from 1: 2 to 1.1: 2.0. _4_ 3425732 Process according to Claims 1 to 5, characterized in that the ratio of anion exchanger / anhydride ranges from 0.1 g to 50 g, preferably 10 g to 20 g, per mole of anhydride.